Manufacture of disazo-dyestuffs containing copper in complex union



Patented May 15, 1951 UNITED STATES PATENT OFFICE MANUFACTURE OF DISAZO-DYESTUFFS CONTAINING UNION COPPER IN COMPLEX Jack Arnold Schedler, Wilmslow, and Roy Whalley, Edenfield, England, assignors to The Clayton Aniline Company Limited, Manchester,

England No Drawing. Application May 27, 1947, Serial No. 750,870. In Great Britain April 11, 1947 5 Claims.

one molecular proportion of a tetrazotised aromatic diamine containing an alkoxy-group in ortho-position to each diazo-group in an alkaline medium with two molecular proportions of an amino-naphthol sulphonic acid or with one molecular proportion each of an aminonaphthol sulphonic acid and a naphthol sulphonic acid, and heating the resulting dyestuff with a solution which contains Cu(NH3)4-- ions until the alkoxy groups have been split up. Solutions of this kind are obtained by mixing solutions which contain Cu" ions, such as solutions of cupric chloride, cupric sulphate, cupric nitrate, cupric acetate, etc. with an excess of ammonia. In-

stead of using solutions of cupric salts as starting materials, cupric hydroxide or freshly prepared cupric oxide may be dissolved in ammonia solution. In all these cases compounds are formed which in an aqueous medium furnish Cu(NH3)4" ions, that is to say, cupritetrammine ions. Instead of inorganic cupritetrammine compounds, organic cupritetrammine compounds may be used; these are formed in known manner by the reaction of a cupric salt or cupric hydroxide with an organic base such as methyl- III amine, ethylamine, pyridine, piperidine or morpholine.

We have observed that in the above process, in the case of many aminonaphthol sulphonic acids, there is a tendency for the dyestufi inoiecule to be destroyed to a certain extent during the ammoniacal cupration, so that the isolated complex copper compound of the dyestuil may be contaminated in some degree by undesired byproducts which affect the purity of colour of the dyeings obtained with the complex copper compound. In many cases, especially in the case of l-amino 8 hydroxynaphthalene sulphonic acids of which the amino group is not protected by a sulpho group in 2-position, as in 1:S-aminonaphthol-S:S-disulphonic acid, it has been found impossible, even after repeated purification, to obtain the complex copper compound in a sufiiciently pure state. In the case of 1:8-amino-naphthol-2zi-disulphonic acid,

however, a reasonably pure complex copper compound is obtained. This acid is also known to differ from most other aminonaphthol sulphonic acids in that it cannot readily be acylated at the NI-Iz group.

According to the present invention disazodyestuifs containing copper in complex union are made by hydrolysing the acylamino groups of cuprifcrous dyestuffs which, in the free form, correspond to the formula wherein R1 stands for a naphthalene nucleus which in addition to an acylamino group contains at least one sulpho group, the -OCu-O- bridge being connected to one of the carbon atoms of a 1:2-position of the naphthalene nucleus and the -N=Nbridge to the other of such carbon atoms, and wherein R2 stands for the radical of a coupling component in which the O--CuO-bridge and the N=N-bridge are linked to vicinal carbon atoms. The cupriferous dyestufis required for this purpose are made by coupling one molecular proportion of a tetrazotised 3 :3 -dialkoxy-4 4' -diamincdiphenyl in an alkaline medium with (a) two molecular proportions of an acylamino-naphthol monoor di-sulphonic acid, or (b) one molecular proportion each of two diiferent coupling components of the kind specified under (a), or (0) one molecular proportion of a coupling component specified under (a) and one molecular proportion of a coupling component of another kind containing a hydroxyl group and capable of coupling in ortho position with respect to the said group but being free from NHz-groups, or (12) one molecular proportion of a coupling component of the kind specified under (a) and one molecular proportion of 1:8-aminonaphthol- 2zi-disulphonic acid, heating the resulting disazo-dyestufi with a solution of one of the above described cupritetrammine compounds until the alkoxy-groups have been split up. The hydrolysis of the cupriferous disazo-dyestuffs so obtained is carried. out by heating them in the presence of a dilute solution of a caustic alkali or of a strong mineral acid. In this manner it is possible to obtain dyestuffs which are in a purer state and dye textile materials in tints of greater purity than the copper cornpounds obtained by cuprating the dyestuffs made from the corresponding non-acylated aminonaphthol monoor di-sulphonic acids.

There is advantageously used as the tetrazocomponent 3 3 -dimethoxy-4 4' -diaminodiphenyl.

As acylamino-naphthol monoor di-sulphonic acids there may be used the acylamino-derivatives of aliphatic or aromatic acids, such as formic acid, acetic acid, propionic acid, maleic acid, succinic acid, benzoic acid or pyridine-3- carboxylic acid. Such coupling components are, for example, N-acetyl-l 8-aminonaphthol-3 6- disulphonic acid, N-acetyl-l:S-aminonaphthol-' 4 6-disulphonic acid, N-acetyl-Z S-aminonaphtl1ol-3 6-disulphonic acid, N-acetyl-2 5-aminonaphthol-Y-sulphonic acid or N-acetyl-3z5-aminonaphthol-T-sulphonic acid; and also l-benzoylamino-, l'maleylamino l-succinylaminoor 1- (3'-pyridinecarboxyl) amino 8 hydroxynaphthalene-3:6-disulphonic acid. As acylaminonaphthol monoor di-sulphonic acids there may also be used the corresponding carbamic acid ester derivatives (urethanes), for example, N carbethoxy 1 :8 aminnaphtho1-3z6-disu1- phonic acid or N-carbethoxy-2:5-aminonaphthol-T-sulphonic acid; and it is to be understood that the term acylamino is used herein to include carbalkoxyamino.

As coupling components containing a hydroxyl group and capable of coupling in ortho-position with respect to the said group, other than acylaminonaphthol monoor di-sulphonic acids, there may be used hydroxy-compounds of the naphthalene series, such as naphthol monoor di-sulphonic acids, for instance, 1:4-naphthol sulphonic acid, 1 :5-naphth0l sulphonic acid, 2:4- naphthol sulphonic acid, 1:3:6-naphthol disulphonic acid, 1 8-aminonaphthol-2 :4-disulphonic acid or N-phenyl-Z 5-aminonaphthol-7-sulphonic acid; hydroxy-compounds of the benzene series, for example, l-hydroxy-B:4-dimethylbenzene or resorcinol; or pyrazolone compounds, for

1 example, 1- (4'-sulphophenyl) -3-methyl-5-pyrazolone.

The cupriferous disazo-dyestuffs obtained in accordance with the invention dye textile materials in various tints which are fast to light. Especially valuable are the dyestufis which produce blue dyeings and which contain at least once the radical of a 1:8-aminonaphthol-sulphonic acid, and among these dyestufis principally those which are derived from 1:8-aminonaphthol-3:S-disulphonic acid. These dyestuffs are obtained by hydrolyzing the acylaminogroups of cupriferous dyestufis which, in the free form, correspond-to the general formula AcylNH O-Cu-O V O-GuO N:N -N=N HOaS- -s 05H wherein R2 stands for a naphthalene nucleus carrying at least one sulpho-group and having the -OCuO-bridge connected to one of the carbon atoms of a lz2-position and the -N:N--v bridge to the other of such carbon atoms, and

wherein the sum of the SO3H-groups is at least 3 and not more than 5. Finally, there are also i 4 thol-3z6-disu1phonic acid, for example, those in which the grouping represents an atom grouping such as -SO3H =N- sogn SO3H scan.

Among such products, special mention may be made of those in which the number of sulpho groups is equal to that of the auxochromic groups (NI-l2 and OH groups) of the coupling components as in the case of 1:8-aminonaphthol-2:4- disulphonic acid, l-hydroxynaphthalene-5 sulphonic acid or 2-hydroxynaphthalene 4- or -6,- sulphonic acid.

The following examples illustrate the invention, the parts being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the litre.

Example 1 24.4 parts of 3:3-dimethoxy-4:4'-diaminodiphenyl are tetrazotised and coupled with 75.8 parts of N acetyl 1:8 aminonaphthol-3:6-disulphonic acid in a solution rendered alkaline with sodium carbonate. The isolated dyestufi is suspended in 3000 parts of hot Water and 88 parts by volume of ammonia solution (specific gravity 0.88) are added followed by a solution Of 60 parts of crystalline copper sulphate dissolved in 200 parts of water. The mass is stirred at a temperature of C. in a reflux apparatus for 22 hours during which the reaction mass is maintained alkaline, if necessary, by further additions of ammonia solution. At the end of this period the complex copper compound is precipitated by the addition of little sodium chloride and isolated. The two N-acetyl groups are hydrolysed by heating the dyestuff with 1150 parts of dilute caustic soda solution of 3-4.- per cent. strength for one hour at -190" C. After neutralising the excess of caustic soda with concentrated hydrochloric acid, the dyestuff is salted out with sodium chloride, filtered and dried. The complex copper the free state, to the formula and is a dark powder, which is readily soluble in water to give a greenish blue solution, and dyes cotton from an alkaline bath bright green-blue tints of very good fastness to light. The dyestuff so obtained is considerably purer than th product of Example 9 of French Patent No. 888,249. Thus, if solutions of 0.15 per cent. strength of these two dyestuffs rendered alkaline with sodium carbonate or caustic soda are tested by dipping a strip of blotting paper in them (canillary analysis), the product of the present ex- 6 with ammonia throughout. The complex copper compound is precipitated by acidification with hydrochloric acid, and separated by filtration. The N -acetyl group of the dyestuif is hydrolysed by heating with 1250 parts of caustic soda solution of 3-4 per cent. strength for 1-1 /2 hours to 90-95" C. After neutralizing the excess of caustic soda with concentrated hydrochloric acid, the dyestufi is salted out with sodium chloride. The complex copper compound which, in the free state, very probably corresponds to the formula is readily soluble in water to give a blue solution. It dyes cotton from an alkaline bath bright reddish blue tints of very good fastness to light.

By using in this example N-pheny-l-2z5-aminonaphthol-7-sulphonic acid, instead of 1:4- naphthol sulphonic acid, a dyestuff giving a still redder shade of blue is obtained. When 1:3:6-

naphthol disulphonic acid is used as second component a dyestuii giving distinctly greener shades is obtained. By using, in this example, instead of 1:4-naphthol sulphonic acid, 1-(4'-sulpho phenyl) -3-methyl-5-pyrazolone or resorcinol two dyestuffs are obtained which, in the free state, very probably correspond to the formulae phonic acid, N-acetyl-Z:5--aminonaphthol-7-sulphonic acid or N-acety1-3:5eaminonaphtho'l-7- sulphonic acid. The dyestuffs obtained from the three latter coupling components dye cotton from a bath rendered alkaline with sodium carbonate in tints which are greyish blue, reddish blue and blackish blue respectively.

4 Example 2 24.4 parts of 3:3-dimethoxy 4:4-diaminodiphenyl are tetrazotised in the usual :manner. A cold, concentrated solution of sodium carbonate is then added until the reaction is faintly alkaline to Brilliant Yellow paper. A solution of the sodiumxsalt of 37 parts of N-acetyl-l :S-aminonaphthol-3:6-disulphoni-c acid is then added immediately. When no more tetrazo-compound can be detected, usually after 5-10 minutes, a solution of 23.5 parts of the sodium salt of 1 z-naphthol sulphonic acid is added. The isolated dyestuff is suspended in 2000 parts of hot water and '75 parts by volume of ammonia solution -'(sp.ecific gravity 0.88) are added followed by a solution of 5.1 parts of crystalline copper sulphate dissolved in 1-70 parts of water. The whole is stirred at :a temperature of .80" C. in a reflux apparatus for 2022 hours, the reaction being maintained alkaline and which dye cotton from a bath rendered alkaline with sodium carbonate in tints which are dark blue and blue respectively. All these dyestuffs produce dyeings of excellent fastness to light.

Example 3 parts of crystalline copper sulphate dissolved in 290 parts .of water. The whole is stirred at a temperature of 80 C. in a reflux apparatus for 20-22 hours, the reaction being maintained alkaline with ammonia throughout. The complex copper compound is isolatedby acidification with hydrochloric .or sulphuric acid, salted out with 6.0.) parts of sodium chloride, and separated by ,iiltration. The N-acetyl group of the dyestuif is hydrolysed by heating with 1-100 parts .of caustic 7 8 soda solution of 3-4 per cent. strength for 1-1 droxynaphthalene-3:6-disulphonic acid and then hours at 90-95 C. After making faintly acid with 22.4 parts of 1-hydroxynaphthalene-4-sulto Congo with hydrochloric or sulphuric acid, phonic acid, is suspended in 2000 parts of hot the dyestuil is filtered off. The complex copper water and 75 parts by volume of ammonia solucompound is readily soluble in water to give a 5 tion, and a solution of 35 parts of crystalline greenish blue solution. It dyes cotton from an cupric chloride (C11C122H2O) in 100 parts of alkaline bath bright green-blue tints of very water is added. The reaction mass is then heated good fastness to light. The complex copper comto 80 C. for 24 hours in a reflux apparatus. It pound so obtained very probably corresponds, is then cooled and the complex copper compound in the free state, to the formula o which has formed is precipitated by neutraliza- NHz OCu-O O-Cu-O NHI Hots S0 H In this case also the copper compound is contion with hydrochloric acid and filtered. The siderably purer than the corresponding product residue is introduced into 1250 parts of a sodium obtained by following the procedure described in hydroxide solution of 34 per cent strength and French Patent No. 780,293. Thus, if solutions heated to 90 C. for 60-90 minutes. The excess of 0.15 per cent. strength of these two products of caustic alkali is then neutralized with hydrorendered alkaline with sodium carbonate or causchloric acid, the dyestuff is precipitated with soditic soda are tested by dipping a strip of blotting 25 um chloride, and then filtered. The dyestufi paper in them (capillary analysis), the product thus obtained is the same as that of the first of the present example is distinguished by exparagraph of Example 2. The same dyestufi is hibiting a very considerably smaller amount of obtained if the hydrolysis is performed with hygrey dyeing impurities. drochloric acid of 4 per cent strength.

The same dyestuff is obtained by conducting Quite similar results are obtained when the the hydrolysis with dilute mineral acid solution cupric chloride is replaced by cupric acetate or of 34 per cent. strength for about 1 hour at cupric nitrate, or when cupric hydroxide or cupric 95100 C. oxide is first prepared by causing sodium hydroxide to act on cupric chloride, and the cupric Example 4 hydroxide or cupric oxide is then dissolved in 24A parts of 3:3, dimethoxy 4:4, diamino ammonia solution. Instead of ammonia, monodiphenyl are tetrazotised, and coupled with the methylamme or monoethylamme may be usedsodium salt of 3'? parts of N-acetyl-1z8-amino- Example 6 naphtho1-326-disulphonic acid as described in 109 5 parts of the sodium salt of the asymmetri- Example 2. A solution of the sodium salt of 23.5 1 Cal dyestuff obtamed by Coupling 1 mol of parts of 2:4-naphtliol sulphonic acid is then added. The dyestuff is isolated by salting out, tetmzmsed dlmethxy'4'4 'dlammodlphen' suspended in 2200 parts of hot water, and 88 thal c parts of ammonia solution (specific gravity 0.88) ene 3 6 dlsulphomc a 1d and 1 mol of U amino-h dro n hth v are added followed y & sqhlblon 60 parts are dlSSOYVBG li I 00 p a r t s oi ai e l l l gt l aii l l talllne col p 511113112396 dissolved m 200 parts an ammoniacal copper nitrate solution consisting Water. T Whole 1S Stlrred at a temperature of 48.5 parts of Cu(NO3)z3I-I?O 136 parts by of 80 C. in a reflux apparatus for 20- 2 hou volume of NH3 and 150 parts or" water and heated the reaction being maintained alkaline throughto 804300 for 20 hours The sparinvly soluble out. The 6 p coppe? compolmd 15 isolated complex copper compound is then segarated by by salting out W sodlum chloljlde' filtering with suction, dispersed in 1500 parts of ace yl group of the dyestufi 1S lflydrolysed 3 caustic soda solution of 4 per cent strength and ing with 1650 parts of caustic soda solution of heated to for one hour, during which oper 3- P Centsjirength 9 141/2 hours to 25 H ation the benzoyl group is split off and complete C. After Salt 01117 Wlth 409 parts of 50 mm dissolution occurs. The dyestufi is precipitated chloride the excess of caustic soda is neutralised b th i y e addition of hydrochloric acid and sodium Wlth ilym'ochlonc Sulphunc acld, and the chloride, then filtered and dried. The complex stuff is filtered off. The 001 1 Copper copper compound so obtained, which corresponds pound is readily soluble in water to give a blue to the compound of the first paragraph of solution. It dyes cotton from an alkaline bath ample 3 dyes cotton green. b1ue tints bright blue tints of very good fastness to light.

The complex copper compound, in the free state, Example 7 very probably corresponds to the formula: 111 parts of the sodium salt of the asymmetri- NHZ O-Cu-O O-Cu0 N=N N=N SOaH HO3S SO3H cal dyestuif, which is prepared by coupling 1 mol Example 5 of tetrazotised 3:3-dimethoxy-4;4-diamino-di- The asymmetrical azo-dyestuff, which is obphenyl with 1 mol of 1-maley1amino-8-hydroxytainable by coupling the tetrazo-compound from naphthalene-3:G-disulphonic acid and 1 mol of 24.4 parts of 3:3dimethoxy-4;4-diaminodi- 1:8-amino-hydroxynaphthalene-2:4-disulphonic phenyl with 36 parts of 1-acetylamino-8-hyacid, are dissolved in 3000 parts of water and,

yl with 1 mol of 1-benzoylamino-8-hydroxynaph-' after admixture with 2 parts of an ammoniacal copper acetate solution- (36 parts of C11 [C2H3O212-I-H2O Example 8 110 parts of the sodium salt of the asymmetri cal dyestuff, obtained from 1 mol of tetrazotised 3:3-dimethoxy-4;4'-diamino=diphenyl, 1 mol of 1 (3 pyridine carboyl)" amino 8 hydroxynaphthalene 3:6 disulphonic acid (obtained by the action of 1 mol of pyridine-3-carboxylic acid chloride on 1 mol of l-amino-S-hy' droxynaphthalene 3:6 disulphonic' acid) and then 1 mol of 1-amino-8-hydroxynaphthalene- 2:4-disulphonic acid, are dissolved in 3000 parts of water with the addition of 200 parts of pyridine. This solution is dissolved with 35 parts of crystalline cupric chloride (CuC122I-I2O) in 60 parts by volume of ammonia solution (specific gravity 0.91), and mixed with 150 parts of water, and then heated to 80-90 C. for 16 hours. When the whole has cooled, the precipitated sparingly soluble complex copper compound is filtered off, and, in order to split off the pyridine carboxylic acid radical, heated to 95-100 C. for 6-8 hours with 2000 parts of caustic soda solution of 4 per cent strength. The mass is then neutralized with concentrated hydrochloric acid and the dyestuiT, which corresponds to the formula given in Example 3, is precipitated by the addition of sodium chloride, filtered and dried. It dyes cotton greenish blue tints.

Example 9 A dyebath is prepared with 1 part of the dyestufi obtainable as described in Example 6, 2 parts of sodium carbonate and 2500 parts of water. 100 parts of cotton are entered at 60 CHa-C OITIH OOuO and the bath is heated to 90-95 C. After 4 hour 30 grams of crystalline sodium sulphate are added, and the whole is boiled for a further hour. The cotton is dyed green-blue.

We claim:

1. In a process for the manufacture of a disazo dyestuiT containing copper in complex union, the molecule of which dyestuif tends to deteriorate during ammoniacal cupration, the step of 10 subjecting a cupriferous dyestuff which, in the free form, corresponds to the formula HOaS- -SO2H wherein,R2 stands for a naphthalene nucleus carrying at least one sulpho group and having the OCu-O-bridge' connected to one of the carbon atoms of a 1:2-position and the N N- bridge to the other of such carbon atoms, and wherein the sum of the sulpho groups is at least 3 and at the most 4, to the action of a hydrolyzing agent selected from the group consisting of dilute alkali solution and dilute mineral acid solution, whereby acylamino contained in the said cupriferous' dyestuif is hydrolysed to free amino.

2. In a process for the manufacture of a disazo dyestufi containing copper in complex union, the molecule of which dyestufi" tends to deteriorate during ammoniacal cupration, the step of subjecting a cupriferoufs dyestulf which, in the free form, corresponds to the formula wherein R2 stands for a naphthalene nucleus carrying at least one sulpho group and having the O-CuO-bridge connected to one of the carbon atoms of a 1:2-position and the -N=N- bridge to the other of such carbon atoms, and wherein the sum of the sulpho groups is at least 3 and at the most l, to the action of dilute alkali hydroxide solution, whereby acylamino contained in the said oupriferousdyestuif is hydrolysed to free amino.

3. In a process for the manufacture of a disazo dyestufi containing copper in complex union, the molecule of which dyestuff tends to deteriorate during ammoniacal cupration, the step of subjecting a cupriferous dyestuff which, in the free 0., form, corresponds to the formula to the action of a dilute alkali hydroxide solution, whereby the acetylamino group in the said cupriferous dyestuff is hydrolysed to free amino.

4. In a process for the manufacture of a disazo dyestuff containing copper in complex union, the molecule of which dyestuff tends to deteriorate during ammoniacal cupration, the step of subjecting a cupriferous dyestuff which, in the free form, corresponds to the formula 2,553,011 v 11 12 to the action of a dilute alkali hydroxide solujecting a cupriferous dyestuff which, in the free tion, whereby the acetylamino group in the said form, corresponds to the formula cupriferous dyestuff is hydrolysed to free amino. to the action of a dilute alkali hydroxide solution, 5. In a process for the manufacture of a disazo whereby the acetylamino groups in the said dyestuff containing copper in complex union, the cupriferous dyestuff are hydrolysed to free amino.

molecule of which dyestufi tends to deteriorate JACK ARNOLD SCI-IEDLER.

during ammoniacal cupration, the step of sub- ROY WHAIL)EY.

REFERENCES CITED The following references are of record in the file of this patent: V

UNITED STATES PATENTS Number Name Date 1,767,379 Krzikalla et a1. June 24, 1930 1,849,572 Gyr Mar. 15, 1932 1,849,573 Gyr Mar. 15, 1932 1,889,732 Stusser Nov. 29, 1932 1,921,336 Wiedemann et al. Aug. 8, 1933 1,940,066 Stusser Dec. 19, 1933 2,036,159 Mendoza Mar. 31, 1936 2,243,020 Straub et a1 May 20, 1941 2,400,092 Anderson May 14, 1946 FOREIGN PATENTS Number Country Date 780,293 France Jan. 29, 1935 

1. IN A PROCESS FOR THE MANUFACTURE OF A DISAZO DYESTUFF CONTAINING COPPER IN COMPLEX UNION, THE MOLECULE OF WHICH DYESTUFF TENDS TO DETERIORATE DURING AMMONIACAL CUPRATION, THE STEP OF SUBJECTING A CUPRIFEROUS DYESTUFF WHICH, IN THE FREE FROM, CORRESPONDS TO THE FORMULA 